Dihydrocarbon peroxides capable of controlling polymerization reactions



Patented July 15, 1952 f e UNITED STAT-ESv 2,603,629 Po'lllNTv oFFlcE DInYDRocARBoN PERoXlDlls GAPABLE F coNTRoLLlNG PoLYMERlzATloN REAG- T'IONS This invention pertains' to merizing unsaturated 'organiooom'pounds 'in the presence' of an oxygensc'ontaining compound de rivedv from .polyenic,eyolie hfydro'cai'boiis; 'which is capable of initiatingandaccelerating the polymerization reactionn Sits-initial stages and o'f controllingthe reaction in .the subsequent ooncludingV stages of the polymerization More speciiically, the invention eo'x'icerns la polyliieliisa'- tion 'process involving-unsaturated'organic mono'- mer starting material which thevpolynlerizai tion-is controlled bythe presence of diepolyenio, cyclopentenyl) peroxides 'in admiitu're with 'the reacting monomer or .monomers and also compositions containing 'Said unsaturated org-'allie poly-i merizable compounds'and-said di=(polyen`ie, cyclopentenyl) peroxldes y It is commonly known that unsaturated organioocompounds containing Single oir multiple unsaturated linkages inlay be polymerized with the aid of so-c'alle'd ea'tlytie or initiating agents of the type vreferred to as peroxidic cll'r'iipou'rids containing active oxygen 'groups 'which promote the polymerization reactione especially itl the l'initial stages of the polymerization reaction and,thus, ef?- fectively reduce thelnitial induction period in which the disappearance of reactive monomers from the reaction mixture andthe formation of polymers proceeds "at a slow and'ineillcient rate. Typical ofy such catalysts heretofore utilized inpol'ymerization reactions lare shell compounds as benztvyli peroxide, di-tertiary'bl'ltyl peroxide andy in 'aqueous systems-certain-intallic lsalts y'persulfune aoid These peroxi'de type\-'cata1 y 's-co'fnionly employed .oy the ort many variedpoiyineriza= tion reactions exhibit 'certain deficiencies as wholly desirable! polymerization oataly'stsin that they initiate v'tno reaction chains' 'oy-,trillen 'tile polymerization 'proceeds `lout-lume little )influence on .the concluding stages i of the polymerization reaction lwhen the 'reactlon-'rnayproceed Arapidly and result :in the production of high molecular weight; solid products offtne'pol mentation which may not. be desirabla jle'jhlieriiioreg 'the above indicated peroxide compolllidspresentlyeiiipioyed as catalysts are relatively unstable' vat tempera-a tures above about 100? 13611120" f'Cw, thl'ls .limiting theirl Vrange ofv Opel'ability,` andl- Sonie may'y l's'lilt in the productionchunuesilfably coloedresinolis products.- The didpolyenie,eyclopentenyl) peli-vr stages of thepolynlerlzationito-preyeiit-the'forlne' tion vof undesirably llligll molecular Weight polyi mers, ,the presentlperoitidioicomplnis "are lbfe" vaprocess.lori .poly-f claims.. `(c1. 26o-93.5)

lysts of this type. This dual capacity action of the peroxides of this invention in promoting the polymerization reaction in the initial stages when the induction 'period is desirably reduced and, in f effect, inhibiting the polymerization reaction rate during the final stages of the polymerization when thelate of polymer formation is desirably reduced to prevent the production of the less desirable high molecular weight polymers is believed to result from a change in the structure of the cli-(polyenic cyclopentenyl) peroxides dur'- ing the course of the reaction. y

Accordingly, it is one object of this invention to provide a polymerizationy process employing i an agent which enhances the polymerization in the initial stages and limits the size of the polymers formedin tile-concluding stages of vthe reaction. Another obieotoi the invention is to provide new polymer-liable compositions. Still all' other object of tneinventlon is to provide a polymer-ization controlling agent is soluble in polymerizable oigane monomers; is' Sllbstajm tially colorless, and does not result in the fc'ii'rna tion of colored 'polymeric products.

ln one of its embodiments the present ilifena tion concerns a polymerization prooes's illi'cll comprises 'polymerizing' n unsaturated oigan-io compound at polymerization reaction conditions in the presence of Va'polynle'liaforl control agent comprising a di-(polyenio eyolo'pentenyl nydiocarbon) pelolii'de formed by the' controlled oilitlahi tion of a polyoleinlo cyclic onj'unct polymer hydrocarbon..

A more specific embodiment of the inyentin concerns a lpolyinerization process 'pinion coinp'rises poly-morning ari unsaturated organic coma pound at polymeriation reaction conditions in the presence of from about 0.001 to about 5% by weight of the reaction mixture of a polio'nerizl'tj tion loontnii agent comprising a peroxide formed by aeration of a inixtu'reo'f Vpolyol'eilnic cyclic conjunct polymer hydiocarllonsV at controlled oxidation conditions. 1

` Another specific embodiment of the invention relates to a composition consisting of a mixture of at least onepolymerizable unsaturated organic compound and 'from about o.00 'l to about 5% by Weight of Said mil'itue of a polyln'li'z'aton'n" trol agent comprising a dipoiyeniocyelopentenyl hydrocarbon) peroxide forinedby the controlled oxidation of a polyoleiiriic, cyclic comune-t 4poly-b mel' hydrocarbon. f

The polymerization `controlv agents utilized in the present polymerization process and char-- aeterized herein/as the :product formed by the controlled oxidation of a vmixture of polyoleilnie cyclic co'njllnct polymer. hydrocarbons. containing peroxidic oxygen comprisesa mixture of chemical individuals having the general formula:

lisos-sona conjunct polymers.

wherein R,-reprefs,enting that portion of the -peroxide molecule on either end of the peroxidic oxygen bridge, is a hydrocarbon radical having the structure and composition of the original conjunct polymer hydrocarbons subjectedfto -oxidation less a hydrogen atom ofan alkylor allrenylY side chain of the cyclopentenyl nucleus present in the hydrocarbons containedfin the mixture of.`

contained in the mixture of oxidized conjunct polymer hydrocarbons may be representedmore Y specifically by the formulas:

where the radicalsrRr to Ra .are selected fromv the group consisting of hydrogen and alkyl, alkylene, alkenyl, 'alkenylena alkapolyenyl and alkapolyenylene hydrocarbonradicals, atleast two of the substituents `Rr to R1 are hydrocarbon radicals, not more thantwoof they groups R1, Rs and R7 represent hydrogen radicals, and one R group in each radicaljsselected from the group consisting, of ',alkylene, alkenylene; Aand Vallia` polyenylene. The above formulaA containingike-` tonic `oxygen groups -is believed to be' representative ofzthe general type ,of compoundsv obtained upon deepfseated or prolonged oxidation of "the polyolenic cyclic conjunctpolymer hydrocarbons and arev likewise believed to take part in directing the course of lthe polymerization reaction by virtue of the peroxidic oxygen groups within the` coml29und. i, y s s Y, VvThe hydrocarbon-starting materials which may be oxidized under controlled conditions to form the novel peroxide derivatives thereof hereinabove noted, are Vreferredto asA vunsaturated coniunct polymers having a polyolefinic, cyclic structure,` the .properties, vstructure Yand methods for the preparation of whichare described in US. Patents VNos. 2,413,316, 2,477,038, andv 2,476,955. Briefly, these hydrocarbons, capable of oxidation toform ,the specic peroxidic Y oifzygen` containingpolymerization: catalysts herein providedare formed by the reactionof a conjunctpolymerization catalystl with an unsaturated 'aliphatic or cyclic hydrocarbonor saturated, branched chain aliphatic hydrocarbon, thelreacton being effected et iempsraiuresfrofrm about. to. about 200 C. .whereby a sludgeylike product is formed as The ,peroxidic compound v the iridividilal"coriipone'nt :of the Amiiture of conjunct polymers:

whereiny radicals R and R1 to Rv are selected from the group consisting of hydrogen, alkyl,l

*j alkenyl and alkapolyenyl hydrocarbon radicals and'at least two of the substituents Ra to' R7 are Y hydrocarbon radicals, and not more than two of the groups R, R1, R2', and R7 represent hydrogen. Individual 4components inathefmixture of :unsaturated 'conjunct polymers var-yV7 asl tothe number of g hydrogen, alkyl; xgallrenylf;,andl .alkapolyenyl groups attached tothe cyclopentenyl nucleus, but

in general, the cyclopentenyl nucleus is commonv to all of the Ahydrocarbons in thefloWer-boiling fractions of the mixture, some of the high-er boilv Y ing components containing A-dicyclicnuclei.A The components ofthe mixtureof. unsaturated conjunct polymers vary in molecular vWeight fromA as low as about250 toas high yas about 450, the' highestboiling*fractions oiwhich have molecular Weights as highas 1000and contain from about 2.5 to about 4 double bondsper molecule of which anaverage of from about 15.510 about 2.5 belong tol a conjugated dienic system andthe Vremaining olenic linkages are distributed throughout the hydrocarbon chains in isolatedpositions.

The di- (polyenic cyclic hydrocarbon) peroxides employed as polymerization control agents in the present process forV the polymerization of unsaturatedy organic compoundshmay be produced by several alternative .proceduresa particularly advantageous method of production comprising oxidationof the unsaturatedconjunct polymers by means of ajcontrolled, ,non-explosive, thermal or catalytic oxidation,` preferably employing relatively high pressuresinvthe oxidation reactor within specific temperaturelimitations to prevent theformation of deep seated oxidation products which maybe formed whenthe oxidation reaction isvallowed to proceed uncontrolled.,

s Suitable cat lysts forvhastening the -oxidatio of the unsaturatedV conjunct` polymers'to form the polymerization controlV agents herein pro videdare thehydroha'lides of. ,the halogens, that one product ofthe reaction, from which the f sludge comprise a mixture'of homologous'hydro-` carbons -havingfthe following general structureA molecular weight and the length ofthe side chains attached to the cyclopenterrylnucleus vary among Vin which the individualcomponents vary in s Oxides: atlhisher isfhydrogen'uoride, hydrogen chloride and hydrogen bromide, lor la small amount, up to about 10% by weight o f the hydrocarbons chargedof a previously oxidized mixture of Vunsaturated con.

junct polymers, the presence of `a catalyst in the reaction mixture generally reducingor eliminating the so-called induction .period inrwhich no appreciable reaction of .the hydrocarbons and oxygenoccurs.` The-oxidation; may be effected at atmospheric pressure by bubbling an oxygenfcontaining gas, such asair orvpure oxygen itself through a column of theunsaturated conjunct polymers or at,v superatmospheric pressures by pressurizing vthe oxygen-containing gas in aV stirred pressure autoclave containing the hydrocarbon charge. vIt is found' that oxidation of the unsaturated conjunct' polymers proceeds at temperatures even be1ow;0C;(s1ow1y, however), to form the di-(polyenic, .cyclic hydrocarbon) peroxides `while l200jC. is generallyxthe upper temperature limitation v, to.: :obtain: the -desired 1con'- trolled: oxidation of the: unsaturated conjunct polymers and .theiormation of thepresen't 4pertemperatures,V degradation oc- 51 curs- 'A' Suitable .diluent Iier-.be added to. the mixturev ofunvsaturated conjunct polymers prior to oxidationfto-provide greater control over the react ion',suchT diluents generally comprising the saturated hydrocarbonsand halogenated hydrocarbons, preferablyia relatively volatile n-parafiin which may berenioved from the oxidation re-V action'mixtureat *lowv temperatures following the oxidation.. Y

l.Chieti themeferred mthodsof preparing the' dirpolyenic cyclic.-hydrocarbon), peroxides com-- prises .heating ,a mixture of gaseous oxygen and the unsaturated` conjunct polymer hydrocarbon reactant ata pressure of from about 2 to about 30l -atmospheres.;fand `at* a temperature of from about 50 to about 150 C. in the presence of.

depending upon the degree of oxidation desired.

A Another suitablemethod for the, preparation of the; presente-peroxides utilizablev as polymerization :control agents vin the aforementioned :oxidationmethodvcomprises. bubbling. an oxygen-containing gas such as air,`.or pure oxygen, into a mixture ofthe unsaturated :coniunct polymers for a reaction period suitable `to obtain the desiredl degree .of oxidation. The oxygen-containinggas is desirably introduced intothe hydrocarbon chargel containedin an elongated verticalA column andpreferably into the bottom of said co1umn, .permitting the gas bubblesA to. rise throughV thecolumn in contact withr the hydrocarbons; The rate of oxidation maybe increased by extending lthe height of the column and re-v ducing the size. of the bubbles thereby increasingthe time and area of contact of the voxygen containing gas with the hydrocarbon charge. When effected at room temperature or below, the latter method produces .a suitable mixture of peroxides in a period of time of from about 24 hours to about 10days. Distillation, extraction, or other methods of removal may be employed to separate the.- excess. reactant hydrocarbons or inert diluent from-the oxidation reaction mixture.

Polymerizable monomers which may be utilized as charging stocks, in the present polymerization reaction, catalyzed by the aforementioned di (polyenic cyclic hydrocarbon) -peroxides are characterized'as unsaturated organic compounds, wherein vtheunsaturation is of the olefinic, polyolenic, or Aacetylenic type. Polymerization, as referredV to herein includes not only simple polymerization between monomers ofthe same structurei and composition, but also includes heteropolymerization or co-polymerization between two or more diverse polymerizable monomers. Y Polymerization is-eifected by admixing or dissolving from abont.0.001.to .about 5% by weight of the polymerizable'y -rmonomers of the y present` di- (polyenicficyclicihydrocarbon) peroxide into a mixturev ofithemonomers and heating-theresulting mixtureito a `temperature of from about 50 to. about 200 C., -and preferably from about '70 toabout1209C.. i 1 if p'lhamanyoreanio compounds recognized byv they art as polymerizable monomersmay be each independently and in adm-ixture utilized as.charg.

ing stock in the-presentipolymerization process. Of the classes.offcompoundsrepresented as unsaturated polyrnerizable monomers, perhaps the largestl single class of. compoundsy readily subject tok peroxide catalyzed pt alyn'lerization are the organiccompounds containing mono-oleiinic un.- saturation such as vinyl alcohol-esters, ,the vinyl halides, the vinyl aromatic compounds such as `styrene, vand alphamethylstyrene, vinyl .ethers,

vinyl kctones, and other ..v;inyl derivatives; the corresponding allyl compounds, derivatives .of acrylic acid, such asjacrylonitrile, and its many saturated and unsaturated alcohol esters; and

alpha-substituted acrylic acid derivatives; theV mono-olenic hydrocarbons, such yas ethylene, propylene, butylene, etc.: cyclic` unsaturates such as inden or coumarone; and other compounds, within the generalclass of mono-oleiinic unsaturated organic compounds.

Another large and .importantmclass of poly-y i drying oils, etc., are.generallyhydrocarbons, but

may also contain other substituents such as halogen, amino, nitro,.carboxyl, carbonyl, and ester groups, yielding polymers of diverse properties.V

Representative compoundswithin the latter class of polymerizableI monomers comprise the polyenic hydrocarbons such as butadiene-1,3, isoprene, cyclopentadiene, substituted dienes such as 2-chlorobutadiene1,3, and lcompounds of vsimilar structure.. When copolymerized withother .unsaturated monomers,

aiectftheipolymerization such .as acids or bases'Y such 'asstyrena isobutylene. etc., the dienes, and especially theconjugated dienes, yield .elastomeric products generally characterized as synthetic rubbers.

Still other polymerizableby means of the present di-(polyenic cyclichydrocarbonlperoxides include the unsaturated aliphatic alcohol andunsaturated aliphatic acid inter-esters or the esters of saturated aliphatic alcohols and acids and unsaturated alcohols and acids and the unsaturated alcohol ethers of saturated or unsaturated alcohols.

Typical of such compoundsare the glyceride fatty acid Y esters, such as' 'glycerol nono-, di-, and

trilinolenate and others.v These organic corn-V pounds may-also contain other-.diverseA` groups,

such as amino, nitro, halogen, sulfate, phosphate, 'and other groups which in themselves do not affect the polymerization reaction, but introduce modifications inthe physical and chemical properties ofthe resulting polymeric products, such fas their solubility in various solvents, their melting points, and their reactivity with other reagents. Y

The present peroxide catalysts are utilizable in any of the various systems of polymerization utilized in the art; that iS...I.1 bulk polymerization, wherein one or moreof the monomers is admixed with theV .peroxide polymerization; catalyst and thereaterheated tothe desired temperature and pressure conditions eiectL polymerization thereof and in ywhich.` system other' agents which divinylbenzene, the `halogen unsaturatedorganic compounds original unsaturated yconjunct lp'oly'rr'rery hydroat `45311215.4102 s. if. Agu.' va'ldfstirred.1211725C.'until oxygen' absorption A by' the hydrocarbon lmixture ceased, at the endoi'about iirhoursv ofY contact. The oxidation product again contained approximately lmole -of oxygen per mole 'of-unsaturated conjunct polymer charged and upon analysis :had an oxygen content 'of-approximately 10%. This product likewise contained approximately of the oxygen contained therein as non-di-tertiary alkyl peroxidev by the titanous chloride titration method and approximately '50% of the oxygen as di-tertiary alkyl peroxide by the spectrographic method of analysis, j

Example III Although oxidation 'of unsaturated conjunct polymer -hydrocarbons generally ceased or proceeded at a greatly retarded 'rate afterthejaddition of approximately one mole vof oxygen per mole of said unsaturated polymer in the absence of extraneous catalytic effects, further oxidation could be obtained by contacting the unsaturated conjunct polymers with oxygen in the presence of a hydrogen halide, such as hydrogen iiuoride or by irradiation with ultra violet light.

The product obtained with the aid of a hydrogen halide or irradiation may contain up to about 2 moles of oxygen per mole of unsaturated conjunct polymer, a much higher proportion of the oxygen appearing as ketonic oxygen than the product obtained upon oxidationY in the absence of hydrogen halide or ultra violet radiation. Furthermore, deep-seated oxidation products begin to appear after the absorption of 1 mole of oxygen per mole of unsaturated conjunct polymer, such as carbon dioxide, carbon monoxide, and low molecular weight acids, ketones, and alcohols.

The ability of the peroxidic compound prepared by the oxidation of the unsaturated conjunct polymers to control the polymerization of an unsaturated monomer is shown in the following Example IV wherein the oxidation product prepared as in Example I above, (that is, the oxidized unsaturated conjunct polymer prepared by aeration of the hydrocarbons) is utilized to control the polymerization of styrene.

Eample IV Two series of styrene samples, each of which was approximately cc. in volume, one series consisting of uncatalyzed styrene and the other consisting of styrene containing 0.75% by weight of the peroxide polymerization control agent prepared as in Example I above, were placed in glass tubes approximately 13 centimeters long and 15 mm. in diameter. Each series of tubes (that is, the control samples consisting of only styrene and the samples consisting of styrene and 0.75% by weight of the unsaturated conjunct polymer hydrocarbon peroxide) was uniformly heated in pairs in a constant temperature bath, one pair at 25 C., a second pair at 38 C., a third pair at 71 C., and a fourth pair at 100 C. The extent oi polymerization was determined in each pair of samples by measurement of the viscosity of the styrene in each of the control and sample tubes, vthe relative ivilscosity oi the controllanti test samples -bein'gfoinparedby tl'iebubble time for each pairloftubes at thev same'polyinerizae tion temperature.' ItV was'foundfthat at 257`a'nd 'at 38 C.;- "the unsaturated vconjunct polymer peroxides. markedly increased`v the 'rate' o poly-I -rner'ization of thefstyrene in/ the test samples,

of polymerization were aboutthe-same for'the' catalyzedlandtlfi'e uncataly'zed-mixtures It is apparent thatwas the rateof thermal polymeriza- `tionbecomes highielat the higher l'tempera'- tures) the'peroxide induced reaction'becomes of relatively small significance? as a factor in ydetermining the overall polymerization rate. On the other hand, at the lower temperatures, at which the rate of thermal polymerizationY is low, the peroxide-induced lpolymerization accounts for the bulk of the reaction in the initial stages.

At all four temperatures, as the reaction proceeded, a time wasreachedat which vthe rateof the uncatalyzed reaction began to .exceed `@that of the peroxide-catalyzed reaction. .fIhisftime was about 300 hours at 25 C., aboutllOO hours at 38 C., Vabout 20,hoursat .71 andabout 2 hours at C. -At these points,v atfwhich the over-al1v rate of polymerizationbecam'e high at all four temperatures,.thefregulating effect oi the present peroxides became manifest. Either by the effect of some materials originally present in the air-blown conjunct polymers or because of some materials formed in the decomposition of the peroxides, a mild chain-breaking effect is exerted which prevents the peroxide-induced reaction, in its later stages, from reaching the high and uncontrollable velocity of the uncatalyzed reaction of a polymerization induced by conventional peroxides. This mild inhibiting eiect, which, like the initial catalyzing effect, is more pronounced at the lower thanV at the higher temperatures, permits easy control of the reaction in its later stages and makes possible the consistent recovery of polymer in intermediate stages of polymerization which could normally be obtained only with great diculty.

Although I have shown the present peroxides to be useful mainly for inducing the polymerization of unsaturates, it is apparent that they may be used for other peroxides induced reactions as well, such as the addition of saturated alkyl polyhalides to oleflnes, the condensation of acetic acid or its derivatives to the corresponding succinic compounds, the condensation of toluene to dibenzyl, and the like.

I claim as my invention:

l. A polymerization control agent comprising a peroxide of a hydrocarbon having the following general structure:

ltr-C fl-R1 R1, R2 and R1 being hydrogen, said hydrocarbon having a molecular weight of from about 250 to about 1000 and containing from about 2.5 to about 4 double bonds per molecule of which pounds an average of from about l1.5 to about 2.5 belong to a conjugated dienic system and the remaining oleiinic linkages are distributed throughout lthe hydrocarbon chains in isolated positions. 2. A process for the polymerization of an unsaturated polymerizable organic compound selected from the group consisting of compounds containing ethylenic unsaturation and. Y comcontaining` acetylenic unsaturation, which -comprises subjecting said compound to polymerization reaction conditions in the presence of a polymerization control agent comprising a peroxide of a hydrocarbon having the following general structure:

*Y v' Rx lRz AR1 c n.

Y Y: Y q -RFCT-RJ Y wherelnl'tand R1 to .,Rf are selected from the group consisting of hydrogen, alkyl, alkenyl and alkapolyenylV lhydrocarbonV radicals, at least two of the groupsrRs to R7 being hydrocarbon radir cals and not morerthan two of the groups R, R1, R2 and Pyrbeing hydrogen; said hydrocarbon havingl a molecular weight of from about 250 to about 1000 and containing, from about 2.5 to

' about 4` double bonds per molecule of which an contains. ethylenic unsaturation. Y

Y 5. Thevprocess of Aclaim-2 further characterized in that said polymerizable organic compound is styrene. 1 y

' HERMAN S. BLOCH.

l o REFRENcEs-CITED Y The following references yare of record in the file of this patentiv UNITED STATES PATENTS Number Namev Date 1,683,404 Ostromisle'nsky Sept. 4, `1923 2,430,864 Farkas V Nov. 18, 1947 2,447,794 Brewer Aug. 24, 1948 2,472,152

Farkas June 7, 1949 

2. A PROCESS FOR THE POLYMERIZATION OF AN UNSATURATED POLYMERIZABLE ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS CONTAINING ETHYLENIC UNSATURATION AND COMPOUNDS CONTAINING ACETYLENIC UNSATURATION, WHIC COMPRISES SUBJECTING SAID COMPOUND TO POLYMERIZATION REACTION CONDITIONS IN THE PRESENCE OF A POLYMERIZATION CONTROL AGENT COMPRISING A PEROXIDE OF A HYDROCARBON HAVING THE FOLLOWING GENERAL STRUCTURE: WHEREIN R AND R1 TO R7 ARE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL, ALKENYL AND ALKAPOLYENYL HYDROCARBON RADICALS, AT LEAST TWO OF THE GROUP R3 TO R7 BEING HYDROCARBON RADICALS AND NOT MORE THAN TWO OF THE GROUPS R, R1, R2 AND R7 BEING HYDROGEN, SAID HYDROCARBON HAVING A MOLECULAR WEIGHT OF FROM ABOUT 250 TO ABOUT 1000 AND CONTAINING FROM ABOUT 2.5 TO ABOUT 4 DOUBLE BONDS PER MOLECULE OF WHICH AN AVERAGE OF FROM ABOUT 1.5 TO ABOUT 2.5 BELONG TO A CONJUGATED DIENIC SYSTEM AND THE REMAINING OLEFINIC LINKAGES ARE DISTRIBUTED THROUGHOUT THE HYDROCARBON CHAINS IN ISOLATED POSITIONS. 